Manufacturing flexible organic electronic devices

ABSTRACT

A method of forming microelectronic systems on a flexible substrate includes depositing a plurality of layers on one side of the flexible substrate. Each of the plurality of layers is deposited from one of a plurality of sources. A vertical projection of a perimeter of each one of the plurality of sources does not intersect the flexible substrate. The flexible substrate is in motion during the depositing the plurality of layers via a roll to roll feed and retrieval system.

The claimed invention was made by, on behalf of, and/or in connectionwith one or more of the following parties to a joint universitycorporation research agreement: Regents of the University of Michigan,Princeton University, The University of Southern California, and theUniversal Display Corporation. The agreement was in effect on and beforethe date the claimed invention was made, and the claimed invention wasmade as a result of activities undertaken within the scope of theagreement.

FIELD

In a number of embodiments, devices, systems and methods hereof relateto organic electronic devices including, for example, organiclight-emitting diode devices and manufacture thereof.

BACKGROUND

The following information is provided to assist the reader inunderstanding technologies disclosed below and the environment in whichsuch technologies may typically be used. The terms used herein are notintended to be limited to any particular narrow interpretation unlessclearly stated otherwise in this document. References set forth hereinmay facilitate understanding the technologies or the background thereof.The disclosure of all references cited herein are incorporated byreference.

Opto-electronic devices that make use of organic materials are becomingincreasingly desirable for a number of reasons. Many of the materialsused to make such devices are relatively inexpensive, so organicopto-electronic devices have the potential for cost advantages overinorganic devices. In addition, the inherent properties of organicmaterials, such as their flexibility, may make them well suited forparticular applications such as fabrication on a flexible substrate.Examples of organic opto-electronic devices include organic lightemitting devices (OLEDs), organic phototransistors, organic photovoltaiccells, and organic photodetectors. For OLEDs, the organic materials mayhave performance advantages over conventional materials. For example,the wavelength at which an organic emissive layer emits light maygenerally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage isapplied across the device. OLEDs are becoming an increasinglyinteresting technology for use in applications such as flat paneldisplays, illumination, and backlighting. Several OLED materials andconfigurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full colordisplay. Industry standards for such a display call for pixels adaptedto emit particular colors, referred to as “saturated” colors. Inparticular, these standards call for saturated red, green, and bluepixels. Color may be measured using International Commission onIllumination (CIE) coordinates, which are well known to the art.

One example of a green emissive molecule is tris(2-phenylpyridine)iridium, denoted Ir(ppy)₃, which has the following structure:

In this structure, we depict the dative bond from nitrogen to metal(here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as wellas small molecule organic materials that may be used to fabricateorganic opto-electronic devices. “Small molecule” refers to any organicmaterial that is not a polymer, and “small molecules” may actually bequite large. Small molecules may include repeat units in somecircumstances. For example, using a long chain alkyl group as asubstituent does not remove a molecule from the “small molecule” class.Small molecules may also be incorporated into polymers, for example as apendent group on a polymer backbone or as a part of the backbone. Smallmolecules may also serve as the core moiety of a dendrimer, whichconsists of a series of chemical shells built on the core moiety. Thecore moiety of a dendrimer may be a fluorescent or phosphorescent smallmolecule emitter. A dendrimer may be a “small molecule,” and it isbelieved that all dendrimers currently used in the field of OLEDs aresmall molecules.

As used herein, “top” means furthest away from the substrate, while“bottom” means closest to the substrate. Where a first layer isdescribed as “disposed over” a second layer, the first layer is disposedfurther away from substrate. There may be other layers between the firstand second layer, unless it is specified that the first layer is “incontact with” the second layer. For example, a cathode may be describedas “disposed over” an anode, even though there are various organiclayers in between.

As used herein, “solution processible” means capable of being dissolved,dispersed, or transported in and/or deposited from a liquid medium,either in solution or suspension form.

More details on OLEDs, and the definitions described above, can be foundin U.S. Pat. No. 7,279,704, which is incorporated herein by reference inits entirety.

Most rigid OLEDs are formed on a glass substrate and encapsulated with aglass or metal plate, sealed around the edge with a bead of adhesivesuch as UV-curable epoxy. Some work has been published on flexibledisplays encapsulated with a thin film moisture barrier depositeddirectly on top of the OLED. In those cases, the barrier is either aninorganic thin film or a composite organic-inorganic multilayer stack.Organic-inorganic stacks are particularly good at covering particulatedefects on the OLED surface (however, at the expense of a longer TACtime and more complex material structure).

OLEDs may find use in a range of applications including, for example,displays, signage decorative lighting, large area flexible illumination,automotive applications and general lighting. In general, it is believedthat significant price savings can be achieved in OLED manufacturingusing roll-to-roll processing. In that regard, throughput is relativelyhigh in such processes. Moreover, relatively inexpensive metal foils andplastic webs may be used as substrates.

A roll-to-roll fabrication process methodology and system 10 is setforth in FIG. 1. In FIG. 1, a substrate 20 is unwound from a substratefeed roller 22, fed to a roll coating roller 24, and undergoes plasmapretreatment with a linear ion source 14. Fourteen vacuum organicevaporator stations 40 a-40 n are positioned around roll coating roller24 as illustrated in FIG. 1. A DC-magnetron 50 for sputtering and twometal evaporators to deposit a cathode follow organic evaporatorstations 40 a-40 n to form OLEDs on a device side or surface 30 ofsubstrate 20. After OLED deposition thereon as described above,substrate 20 is wound upon a retrieval roller 82. During rolling orwinding upon retrieval roller 82, substrate surface 30 is enveloped by aprotective liner film or interleaf liner 70 provided from roll 72 in anattempt to reduce surface damage of the sensitive organic layers.

A mobile roll transfer box (not shown) allows roll transfer of theretrieval roller 82 between system 10 and a lamination unit (not shown)under inert conditions in an attempt to limit overall H₂O and O₂exposure during the transfer. A roll-to-roll encapsulation unit isoperated under inert atmosphere, and a roll-to-roll optical inspectionsystem provides for defect characterization.

BRIEF SUMMARY

In one aspect, a method of forming microelectronic systems on a flexiblesubstrate includes depositing a plurality of layers on one side of theflexible substrate. Each of the plurality of layers is deposited fromone of a plurality of sources. A vertical projection of a perimeter ofeach one of the plurality of sources does not intersect the flexiblesubstrate. The flexible substrate is in motion during the depositing theplurality of layers via a roll to roll feed and retrieval system. In anumber of embodiments, a vertical projection of a perimeter of at leastone of an inspection system or a treatment system does not intersect theflexible substrate. The flexible substrate may, for example, besupported upon a generally cylindrical support roller during thedepositing of the plurality of layers. The method may, for example,further comprising cooling.

In a number of embodiments, at least one of the plurality of layers isselected from the group consisting of an insulating layer, an organiclayer, a conductive layer, and an encapsulation layer. At least one ofthe plurality of layers may, for example, be deposited from one of theplurality sources at an angle that is neither horizontal nor vertical.In a number of embodiments, multiple organic thin film layers aredeposited and at least one of two electrodes of the microelectronicsystems is deposited. The flexible substrate may, for example, include apre-patterned electrode. The multiple organic thin film layers aredeposited between the two electrodes. A thin film encapsulation layermay, for example, be deposited on top of the multiple organic thin filmlayers and the two electrodes. In a number of embodiments, the multipleorganic thin film layers, the two electrodes and the thin filmencapsulation layer are deposited under vacuum. The multiple organicthin film layers, the at least one of two electrodes and the thin filmencapsulation layer are deposited without breaking vacuum.

The method may, for example, also include applying a surface treatmentbefore depositing any of the multiple organic thin film layers. In anumber of embodiments, the at least one of the two electrodes isdeposited before any of the multiple organic thin film layers. In anumber of embodiments, at least one barrier layer is deposited beforeany of the multiple organic thin film layers.

The microelectronic system may, for example, be wound upon a retrievalroller after deposition of the at least one thin film encapsulationlayer. The surface of the microelectronic system may, for example, belaminated before being wound upon the retrieval roller. In a number ofembodiments, the flexible substrate is unwound from a feed roller beforedepositing a first of the plurality of layers. In a number ofembodiments, the flexible substrate is unwound from the feed roller andthe microelectronic system is wound upon the retrieval roller in asingle unwind and wind cycle.

In a number of embodiments, the microelectronic systems are organiclight emitting diodes. In a number of embodiments, the method furtherincludes unwinding the flexible substrate from a feed roller and windingthe organic light emitting diodes formed on the flexible substrate on aretrieval roller. As described above, multiple organic thin film layersmay be deposited and at least one of two electrodes may be deposited,wherein the multiple organic thin film layers are deposited between thetwo electrodes. A thin film encapsulation layer may be deposited on topof the multiple organic thin film layers and the two electrodes.

In another aspect, a manufacturing system for forming one or moremicroelectronic systems on a flexible substrate includes a plurality ofdeposition sources to deposit a plurality of layers on one side of theflexible substrate, wherein all of the plurality of layers are depositedunder vacuum, and wherein a vertical projection of a perimeter of eachof the plurality of sources does not intersect the flexible substrate.The flexible substrate may be in motion during the depositing of theplurality of layers via a roll to roll feed and retrieval system. In anumber of embodiments, vacuum is not broken during depositing of theplurality of layers. At least one of the plurality of layers may, forexample, be selected from the group consisting of an insulating layer,an organic layer, a conductive layer, and an encapsulation layer. Atleast one of the plurality of layers may, for example, be deposited fromone of the plurality sources at an angle that is neither horizontal norvertical.

In another aspect, a microelectronic system is formed by the process ofdepositing a plurality of layers on one side of a flexible substrate,each of the plurality of layers being deposited from one of a pluralityof sources, wherein a vertical projection of a perimeter of each one ofthe plurality of sources does not intersect the flexible substrate, andwherein the flexible substrate is in motion during the depositing of theplurality of layers via a roll to roll feed and retrieval system. Themicroelectronic system may, for example, be an organic light emittingdiode system.

In another aspect, a method of depositing a material at less thanatmospheric pressure onto a moving substrate web includes delivering thematerial into an interior of at least one cylinder. The cylinderincludes at least one opening therein through which the material maypass to exit the interior of the cylinder. The method further includesrotating the cylinder so that the material passes through the at leastone opening to be deposited upon the moving web in a determined pattern.The pressure may, for example, be between 10 to 10⁻⁸ torr or between10⁻⁴ to 10⁻⁷ torr. The source of the material may, for example, bepositioned within the cylinder. In a number of embodiments, an axis ofthe cylinder is generally perpendicular to a direction of motion of theweb.

The speed of the web may, for example, be programmable. The rotationalspeed of the cylinder may, for example, programmable.

In a number of embodiments, the cylinder includes a plurality ofopenings through which the material may pass to be deposited upon theweb. In a number of embodiments, the determined pattern includes atwo-dimensional matrix.

In a number of embodiments, microelectronic systems are formed on theweb. The material may, for example, be an organic material or aconductive material. The material may, for example, be an evaporativematerial. In a number of embodiments, the determined pattern includesbuss lines over a transparent conductor on the web.

In a further aspect, a system for depositing a material onto a movingsubstrate web includes a system for moving the web, a cylindercomprising at least one opening therein through which the materialwithin an interior of the cylinder may pass to exit the interior of thecylinder at less than atmospheric pressure, and a control system torotate the cylinder in a controlled manner so that the material passesthrough the at least one opening to be deposited upon the moving web ina determined pattern.

In still a further aspect, a substrate web having a determined patternis formed by the process of delivering the material into an interior ofat least one cylinder, wherein the cylinder includes at least oneopening therein through which the material may pass to exit the interiorof the cylinder, and rotating the cylinder so that the material passesthrough the at least one opening to be deposited upon the web in thedetermined pattern as the web is moving. The material is deposited uponthe web at a pressure less than atmospheric pressure.

The foregoing is a summary and thus may contain simplifications,generalizations, and omissions of detail; consequently, those skilled inthe art will appreciate that the summary is illustrative only and is notintended to be in any way limiting.

For a better understanding of the embodiments, together with other andfurther features and advantages thereof, reference is made to thefollowing description, taken in conjunction with the accompanyingdrawings. The scope of the claimed invention will be pointed out in theappended claims.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 illustrates schematically an embodiment of a roll-to-roll vacuumcoating process which includes a winding unit, plasma pre-treatment witha linear ion source, organic linear evaporators, a magnetron and metalevaporators.

FIG. 2 illustrates schematically an embodiment of organic light emittingdevice.

FIG. 3 illustrates schematically an embodiment of an inverted organiclight emitting device that does not have a separate electron transportlayer.

FIG. 4 illustrates schematically an embodiment of a process and systemhereof to deposit organic electronic devices (for example, OLEDs) andencapsulation thin films sequentially under vacuum.

FIG. 5 illustrates schematically another embodiment of a process andsystem hereof to deposit organic electronic devices (for example, OLEDs)and encapsulation thin films sequentially under vacuum.

FIG. 6 illustrates schematically another embodiment of a process andsystem hereof to deposit organic electronic devices (for example, OLEDs)and encapsulation thin films under vacuum, and further includingpretreatment and barrier coating stations/processes.

FIG. 7 illustrates schematically another embodiment of a process andsystem hereof to deposit organic electronic devices (for example, OLEDs)and encapsulation thin films under vacuum, and further includinginspection and treatment stations/processes.

FIG. 8 illustrates the process of FIG. 5, performed around a generallycircular roll coating roller.

FIG. 9 illustrates the process of FIG. 7, performed around a generallycircular roll coating roller.

FIG. 10 illustrates schematically another embodiment of a process andsystem hereof to deposit organic electronic devices (for example, OLEDs)wherein a vertical projection of a perimeter of each of the depositionsources used in forming organic electronic devices does not intersectthe flexible substrate.

FIG. 11 illustrates the process of FIG. 10, performed around a generallycircular roll coating roller wherein a vertical projection of aperimeter of each of the deposition sources used in forming organicelectronic devices does not intersect the flexible substrate.

FIG. 12 illustrates schematically a process performed around a generallycircular roll coating roller wherein a vertical projection of aperimeter of one of the deposition sources used in forming organicelectronic devices intersects the flexible substrate.

FIG. 13 illustrates the process of FIG. 5, performed around a generallycircular roll coating roller, wherein a vertical projection of aperimeter of each of the deposition sources used in forming organicelectronic devices does not intersect the flexible substrate.

FIG. 14A illustrates the process of FIG. 7, performed around a generallycircular roll coating roller, wherein a vertical projection of aperimeter of each of the deposition sources used in forming organicelectronic devices does not intersect the flexible substrate.

FIG. 14B illustrates the process of FIG. 14A, wherein a verticalprojection of a perimeter of each of the deposition sources used informing organic electronic devices as well as perimeters of otherequipment or systems, including pre-treatment equipment and/or systemsin zone 2 and inspection/treatment equipment and/or systems in zone 6 donot intersect the flexible substrate.

FIG. 15 illustrates a process performed around two generally circularroll coating rollers, wherein a vertical projection of a perimeter ofeach of the deposition sources used in forming organic electronicdevices does not intersect the flexible substrate.

FIG. 16 illustrates schematically a process for depositing lines such asmetal buss lines in the direction of a moving substrate.

FIG. 17A illustrates an embodiment of a cylindrical mask hereof.

FIG. 17B illustrates two cylindrical masks hereof in position to depositmaterial on a moving substrate wherein a first cylinder includes asingle opening or slit and a second cylinder includes a plurality ofopenings or slits.

FIG. 18 illustrates an example of a repeatable grid pattern of busslines on a substrate.

FIG. 19 illustrates schematically a process and system in which acylindrical mask may be used for depositing organic material whereinbroken lines represents open mask areas.

FIG. 20 illustrates schematically a process and system in which atwo-dimensional pattern including both parallel lines and perpendicularlines is deposited upon a moving substrate using, for example, multiplecylinders.

FIG. 21 illustrates schematically a process and system in which atwo-dimensional pattern is deposited upon a moving substrate using asingle cylinder.

FIG. 22 illustrates schematically another process and system in which atwo-dimensional pattern is deposited upon a moving substrate using asingle cylinder.

DETAILED DESCRIPTION

The methods, devices and systems hereof can be used in connection withorganic electronic devices generally. A number of representativeembodiments thereof are discussed in connection with representativeembodiments of flexible OLEDs formed in continuous, roll-to-rollprocesses.

Generally, an OLED comprises at least one organic layer disposed betweenand electrically connected to an anode and a cathode. When a current isapplied, the anode injects holes and the cathode injects electrons intothe organic layer(s). The injected holes and electrons each migratetoward the oppositely charged electrode. When an electron and holelocalize on the same molecule, an “exciton,” which is a localizedelectron-hole pair having an excited energy state, is formed. Light isemitted when the exciton relaxes via a photoemissive mechanism. In somecases, the exciton may be localized on an excimer or an exciplex.Non-radiative mechanisms, such as thermal relaxation, may also occur,but are generally considered undesirable.

Early OLEDs used emissive molecules that emitted light from theirsinglet states (“fluorescence”) as disclosed, for example, in U.S. Pat.No. 4,769,292, which is incorporated by reference in its entirety.Fluorescent emission generally occurs in a time frame of less than 10nanoseconds.

More recently, OLEDs having emissive materials that emit light fromtriplet states (“phosphorescence”) have been demonstrated. Baldo et al.,“Highly Efficient Phosphorescent Emission from OrganicElectroluminescent Devices,” Nature, vol. 395, 151-154, 1998;(“Baldo-I”) and Baldo et al., “Very high-efficiency green organiclight-emitting devices based on electrophosphorescence,” Appl. Phys.Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporatedby reference in their entireties. Phosphorescence is described in moredetail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporatedby reference.

FIG. 1 illustrates an embodiment of an organic light emitting device100. The figures are drawn schematically and are not necessarily drawnto scale. Device 100 may include a substrate 110, an anode 115, a holeinjection layer 120, a hole transport layer 125, an electron blockinglayer 130, an emissive layer 135, a hole blocking layer 140, an electrontransport layer 145, an electron injection layer 150, a protective layer155, a cathode 160, and a barrier layer 170. Cathode 160 is a compoundcathode having a first conductive layer 162 and a second conductivelayer 164. Device 100 may be fabricated by depositing the layersdescribed, in order. The properties and functions of these variouslayers, as well as example materials, are described in more detail inU.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated byreference.

More examples for each of these layers are available. For example, aflexible and transparent substrate-anode combination is disclosed inU.S. Pat. No. 5,844,363, which is incorporated by reference in itsentirety. An example of a p-doped hole transport layer is m-MTDATA dopedwith F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. PatentApplication Publication No. 2003/0230980, which is incorporated byreference in its entirety. Examples of emissive and host materials aredisclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which isincorporated by reference in its entirety. An example of an n-dopedelectron transport layer is BPhen doped with Li at a molar ratio of 1:1,as disclosed in U.S. Patent Application Publication No. 2003/0230980,which is incorporated by reference in its entirety. U.S. Pat. Nos.5,703,436 and 5,707,745, which are incorporated by reference in theirentireties, disclose examples of cathodes including compound cathodeshaving a thin layer of metal such as Mg:Ag with an overlyingtransparent, electrically-conductive, sputter-deposited ITO layer. Thetheory and use of blocking layers is described in more detail in U.S.Pat. No. 6,097,147 and U.S. Patent Application Publication No.2003/0230980, which are incorporated by reference in their entireties.Examples of injection layers are provided in U.S. Patent ApplicationPublication No. 2004/0174116, which is incorporated by reference in itsentirety. A description of protective layers may be found in U.S. PatentApplication Publication No. 2004/0174116, which is incorporated byreference in its entirety.

FIG. 2 illustrates an embodiment of inverted OLED 200. The deviceincludes a substrate 210, a cathode 215, an emissive layer 220, a holetransport layer 225, and an anode 230. Device 200 may be fabricated bydepositing the layers described, in order. Because the most common OLEDconfiguration has a cathode disposed over the anode, and device 200 hascathode 215 disposed under anode 230, device 200 may be referred to asan “inverted” OLED. Materials similar to those described with respect todevice 100 may be used in the corresponding layers of device 200. FIG. 2provides an example of how some layers may be omitted from the structureof device 100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided byway of non-limiting example, and it is understood that embodimentshereof may be used in connection with a wide variety of otherstructures. The specific materials and structures described areexemplary in nature, and other materials and structures may be used.Functional OLEDs may be achieved by combining the various layersdescribed in different ways, or layers may be omitted entirely, based ondesign, performance, and cost factors. Other layers not specificallydescribed may also be included. Materials other than those specificallydescribed may be used. Although various layers may be described asincluding a single material, it is understood that combinations ofmaterials, such as a mixture of host and dopant, or more generally amixture, may be used. Also, the layers may have various sublayers. Thenames given to the various layers herein are not intended to be strictlylimiting. For example, in device 200, hole transport layer 225transports holes and injects holes into emissive layer 220, and may bedescribed as a hole transport layer or a hole injection layer. In oneembodiment, an OLED may be described as having an “organic layer”disposed between a cathode and an anode. This organic layer may comprisea single layer, or may further comprise multiple layers of differentorganic materials as described, for example, with respect to FIGS. 1 and2.

Structures and materials not specifically described may also be used,such as OLEDs comprised of polymeric materials (PLEDs) such as disclosedin U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated byreference in its entirety. By way of further example, OLEDs having asingle organic layer may be used. OLEDs may be stacked, for example asdescribed in U.S. Pat. No. 5,707,745 to Forrest et al, which isincorporated by reference in its entirety. The OLED structure maydeviate from the simple layered structure illustrated in FIGS. 1 and 2.For example, the substrate may include an angled reflective surface toimprove out-coupling, such as a mesa structure as described in U.S. Pat.No. 6,091,195 to Forrest et al., and/or a pit structure as described inU.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated byreference in their entireties.

Unless otherwise specified, any of the layers of the various embodimentsmay be deposited by any suitable method. For the organic layers,preferred methods include thermal evaporation, ink-jet, such asdescribed in U.S. Pat. Nos. 6,013,982 and 6,087,196, which areincorporated by reference in their entireties, organic vapor phasedeposition (OVPD), such as described in U.S. Pat. No. 6,337,102 toForrest et al., which is incorporated by reference in its entirety, anddeposition by organic vapor jet printing (OVJP), such as described inU.S. Pat. No. 7,431,968, which is incorporated by reference in itsentirety. Other suitable deposition methods include spin coating andother solution based processes. Solution based processes are preferablycarried out in nitrogen or an inert atmosphere. For the other layers,preferred methods include thermal evaporation. Preferred patterningmethods include deposition through a mask, cold welding such asdescribed in U.S. Pat. Nos. 6,294,398 and 6,468,819, which areincorporated by reference in their entireties, and patterning associatedwith some of the deposition methods such as ink jet and OVJD. Othermethods may also be used. The materials to be deposited may be modifiedto make them compatible with a particular deposition method. Forexample, substituents such as alkyl and aryl groups, branched orunbranched, and preferably containing at least 3 carbons, may be used insmall molecules to enhance their ability to undergo solution processing.Substituents having 20 carbons or more may be used, and 3-20 carbons isa preferred range. Materials with asymmetric structures may have bettersolution processibility than those having symmetric structures, becauseasymmetric materials may have a lower tendency to recrystallize.Dendrimer substituents may be used to enhance the ability of smallmolecules to undergo solution processing.

OLED Devices may further optionally comprise a barrier layer. Onepurpose of the barrier layer is to protect the electrodes and organiclayers from damaging exposure to harmful species in the environmentincluding moisture, vapor and/or gases, etc. The barrier layer may bedeposited over, under or next to a substrate, an electrode, or over anyother parts of a device including an edge. The barrier layer maycomprise a single layer, or multiple layers. The barrier layer may beformed by various known chemical vapor deposition techniques and mayinclude compositions having a single phase as well as compositionshaving multiple phases. Any suitable material or combination ofmaterials may be used for the barrier layer. The barrier layer mayincorporate an inorganic or an organic compound or both. A barrier layermay, for example, comprise a mixture of a polymeric material and anon-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat.Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which areincorporated herein by reference in their entireties. To be considered a“mixture”, the aforesaid polymeric and non-polymeric materialscomprising the barrier layer should be deposited under the same reactionconditions and/or at the same time. The weight ratio of polymeric tonon-polymeric material may, for example, be in the range of 95:5 to5:95. The polymeric material and the non-polymeric material may becreated from the same precursor material. In one example, the mixture ofa polymeric material and a non-polymeric material consists essentiallyof polymeric silicon and inorganic silicon.

Devices fabricated in accordance with embodiments hereof may beincorporated into a wide variety of consumer products, including flatpanel displays, computer monitors, medical monitors, televisions,billboards, lights for interior or exterior illumination and/orsignaling, heads up displays, fully transparent displays, flexibledisplays, laser printers, telephones, cell phones, personal digitalassistants (PDAs), laptop computers, digital cameras, camcorders,viewfinders, micro-displays, vehicles, a large area wall, theater orstadium screen, or a sign. Various control mechanisms may be used tocontrol devices fabricated in accordance with the methods hereof,including passive matrix and active matrix. Many of the devices areintended for use in a temperature range comfortable to humans, such as18 degrees C. to 30 degrees C., and more preferably at room temperature(20-25 degrees C.).

As described above, the materials and structures described herein mayhave applications in devices (for example, organic electronic devices)other than OLEDs. For example, other optoelectronic devices such asorganic solar cells and organic photodetectors may employ the materialsand structures. More generally, organic devices, such as organictransistors, may employ the materials and structures.

The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, arylkyl,heterocyclic group, aryl, aromatic group, and heteroaryl are known tothe art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32,which are incorporated herein by reference.

It will be readily understood that the components of the embodiments, asgenerally described and illustrated in the figures herein, may bearranged and designed in a wide variety of different configurations inaddition to the described example embodiments. Thus, the following moredetailed description of the example embodiments, as represented in thefigures, is not intended to limit the scope of the embodiments, asclaimed, but is merely representative of example embodiments.

Reference throughout this specification to “one embodiment” or “anembodiment” (or the like) means that a particular feature, structure, orcharacteristic described in connection with the embodiment is includedin at least one embodiment. Thus, the appearance of the phrases “in oneembodiment” or “in an embodiment” or the like in various placesthroughout this specification are not necessarily all referring to thesame embodiment.

Furthermore, the described features, structures, or characteristics maybe combined in any suitable manner in one or more embodiments. In thefollowing description, numerous specific details are provided to give athorough understanding of embodiments. One skilled in the relevant artwill recognize, however, that the various embodiments can be practicedwithout one or more of the specific details, or with other methods,components, materials, et cetera. In other instances, well knownstructures, materials, or operations are not shown or described indetail to avoid obfuscation.

As used herein and in the appended claims, the singular forms “a,” “an”,and “the” include plural references unless the context clearly dictatesotherwise. Thus, for example, reference to “a layer” includes aplurality of such layers and equivalents thereof known to those skilledin the art, and so forth, and reference to “the layer” is a reference toone or more such layers and equivalents thereof known to those skilledin the art, and so forth.

As described above, it is believed that significant price savings can beachieved in OLED manufacturing using roll-to-roll processing via, forexample, high throughput and the use of relatively inexpensive metalfoils and polymer webs as substrates. Nonetheless, there are a number ofproblems with current roll-to-roll processes as, for example,illustrated in FIG. 1. For example, the encapsulation of the OLEDs inthat process is done by laminating a barrier film on top of device.However, between the lamination film and the OLED, a thin layer of glueis required at least in the perimeters. The thin glue layer may providea short circuit for moisture and oxygen. To mitigate this problem, aglue with less moisture permeation property can be used along the edgesof the two films. However, this may only slow down the moisture/oxygenpermeation to certain degree. Also, the lamination glue itself containsmoisture or other gases which may damage the device underneath.

Furthermore, contact of a solid material, surface or object with thevarious organic layers, electrodes, etc. after deposition thereof ondevice side 30 of substrate 20 prior to encapsulation thereof can damagedelicate OLEDs and other organic electronic devices. For example,winding flexible substrate 20 into a retrieval roller 22 can causesignificant damage to OLEDs and other organic electronic devices. Inthat regard, layers are brought into mechanical contact with neighboringlayers as a result of winding, which can easily cause damage to thedelicate OLED and other organic electronic devices. Further, oneparticle can cause protrusions in every other layer. Also, relativemovement between neighboring layers can also easily cause damage to theOLEDs. Using an interleaf as described in connection with FIG. 1 mayreduce some of the damage associated with winding, but not eliminate it.Moreover, contact with the surface of interleaf layer 70 of FIG. 1introduces another potential source of damage. Interleaf layer 70 mayalso bring in large particles, causing additional damage. Damage may,for example, also be caused via contact with a tensioning roller orother positioning, tensioning or other devices which contacts deviceside 30 of substrate 20 in certain processes.

Another problem with certain processes such as illustrated in FIG. 1 isthat the depositions system in some of the deposition stations arepositioned above the substrate, significantly increasing the chance forparticles to fall onto the deposition surface. As known in the art,particles can cause defects such as shorts or bright spots in OLEDdevices. For web process of OLEDs, particles are particularly damagingfor two additional reasons. In that regard, thin film encapsulation,which is required for flexible OLEDs, is very sensitive to particles. Asingle defect in encapsulation caused by such particles can result thefailure of the entire device. Moreover, particles may cause protrusionson all the layers that on top or beneath the particles as describedabove (resulting in a much bigger impact than just the device upon whichthe particles are located).

In a number of embodiments of method, devices and systems hereofmicroelectronic systems are formed on a flexible substrate by depositingon the flexible substrate at least one organic thin film layer, at leastone electrode and at least one thin film encapsulation layer over the atleast one organic thin film layer and the at least one electrode. In anumber of embodiments, depositing the organic thin film layer,depositing the at least one electrode and depositing the at least onethin film encapsulation layer each occur under vacuum and withoutwinding around a roller during or between the depositions thereof. In anumber of embodiments, there is no contact of the device side of theflexible substrates (that is, the side or surface upon which depositionoccurs) with any solid surface prior to deposition of the thin filmencapsulation layer. FIG. 4 illustrates a simple representative exampleof a system 300 and method hereof. System 300 includes a flexiblesubstrate delivery system including a feed or source roller 312 fromwhich flexible substrate 310 is unwound and a retrieval roller 322 uponwhich flexible substrate 310 (including, for example, OLED devices ondevice side or surface 320 thereof) is wound after encapsulation. In theembodiment of FIG. 4, there are two basic deposition zones, both undervacuum. In vacuum zone 2, the various layers of the OLED devices orother organic electronic devices, including electrodes and organiclayers are deposited. In vacuum zone 3, thin film encapsulation isdeposited. In the case that substrate 310 already includes a firstelectrode (for example, an indium tin oxide or ITO electrode) deposited,vacuum zone 2 may, for example, be a vacuum thermal evaporation (VTE)zone where multiple deposition sources can be sequentially arranged todeposit materials including, for example, a hole injection layer (HIL),a hole transport layer (HTL), an emissive layer (EML), an electrontransport layer ETL, an electron injection layer (EIL) and thin metalsuch as Al or Ag as a second electrode to form organic electronicdevices. After the OLED or other organic electronic device materials aredeposited, a thin film is deposited in vacuum zone 3 to encapsulate thedevice under vacuum condition.

Inside each of vacuum zones 2 and 3, there are different depositionsources (or stations), as shown in FIG. 4. Because the nature ofroll-to-roll process, linear sources are desirable. The setup for eachdeposition source is determined, for example, by the substrate (forexample, a polymeric web) moving speed, deposition rate and thicknessrequired for each material. If a certain material requires a thicknessthat cannot be achieved by a single source, multiple sources can be usedfor the same material. In a number of embodiments, the flexiblesubstrate can travel only in the direction from the feed roller to theretrieval roller. In other embodiments, the substrate can travel in thedirection from the feed roller to the retrieval roller and in thedirection from the retrieval roller to the feed roller.

In a number of embodiments, zone 1 is a vacuum zone. Zone 4 mayoptionally be a vacuum zone, but better results may be obtained if zone4 is a vacuum zone. Nonetheless, vacuum is not required in zone 4 aslong as zone 4 is controlled environment which protects the OLEDs frommoisture and oxygen. FIG. 5 illustrates a method and system 300 a hereof(including the components of system 300) wherein vacuum is not brokenbetween OLED deposition in vacuum zone 2 and thin film encapsulation invacuum zone 3. In FIG. 5, the OLED devices are always under vacuumbefore they are fully encapsulated, which minimizes the exposure tomoisture and oxygen.

A system such as illustrated in FIG. 1 requires the moving of depositedOLED devices in an inert environment to an encapsulation station. Thewater and oxygen level in a well maintained glove box is, for example,about 1 ppm. A glove box with N₂ environment maintained at 1 ppmhumidity level contains 1 mol H₂O per 10⁶ mol N₂. (1 mol is 6.023×10²³molecules). By using the gas equation pV=nRT, where p is the pressure, Vis volume, n is mols of gas, R is the gas constant, and T is thetemperature, we can calculate the number of mols of N₂ in a glove box at1 atm pressure at room temperature (wherein R is 8.2×10⁻⁵ m³ atm/K/mol).Using the gas equation, we get the number of mols of N₂ per unit volumein the glove box to be 41 mol/m³. This means the number of mols of H₂Owill be 4.1×10⁻⁵ mol/m³ in the glove box with 1 ppm moistureconcentration. On the other hand in a vacuum chamber maintained at 10⁻⁷Torr, the number of mols of gas present per unit volume is 5.4×10⁻⁹mol/m³. The material may, for example, be deposited at a pressurebetween approximately 10 to 10⁻¹⁰ torr. In a number of embodiments, thematerial is deposited at a pressure between approximately between 10⁻³to 10⁻⁷ torr. Usually, moisture content at such pressure is about70-80%, but for simplicity, we will assume that all the gas present iswater vapor. Therefore, the number of mols of H₂O present per unitvolume is also 5.4×10⁻⁹ mol/m³. This value is four orders of magnitudeless than that present in a glove box with 1 ppm moisture concentration.Calculations to estimate the time for a monolayer of water to bedeposited at high vacuum conditions show that, at 10⁻⁷ Torr, it takesabout 10 sec for a monolayer of water to form on the surface. Given thehigh concentration of water in the glove box it will take much less timefor a monolayer to form in the glove box environment than in a highvacuum environment. Therefore, to transfer a finished, butun-encapsulated, device in a glove box type (inert) environment may notbe suitable even if it is maintained at 1 ppm moisture level.

Because substrate 310 is wound after the OLEDs are made andencapsulated, many adverse issues with the system described inconnection with FIG. 1 are resolved. In that regard, the thin filmencapsulation provides total coverage of the OLED devices, leaving nopath for moisture to attack. As set forth above, encapsulation may serveas a barrier layer or coating to limit permeation of, among otherthings, water vapor and oxygen. The degree of impermeability requiredmay differ in different applications. For example, an encapsulation orbarrier layer having a water vapor transmission rate of less than 10⁻⁶g/m²/day and/or an oxygen transmission rate of less than 10⁻² g/m²/dayor less than 10⁻³ g/m²/day may be suitable for protecting OLEDs.Moreover, the encapsulation film provide mechanical protection for theunderlying OLED devices. Further, the thin film encapsulated OLEDdevices are no longer sensitive to following steps or processes in termsof moisture/oxygen exposure.

FIG. 6 illustrates a more complicated system 300 b, which includes thecomponents of system 300 and additional functionality. In system 300 b,substrate 310 first goes through a pre-treatment process whereinsubstrate 310 may, for example, be cleaned and baked to drive outmoisture in zone 2. Other processes such as UV or plasma treatment mayalso be used. When substrate 310 is formed from one or more polymericmaterials, a barrier coating may, for example, be applied in vacuum zone3 to protect the OLEDs from moisture/O₂ attack from the substrate side.In vacuum zone 4 of system 300 b, the OLED organic layers and one orboth electrodes of the OLED devices may be deposited. In the case thatsubstrate 310 does not include a pre-patterned first electrode/anode,for a conventional bottom emission device, a transparent electrode/anodesuch as ITO may be deposited first. In this case, a sputtering tool forelectrode deposition will required its own vacuum environment. After ITOdeposition, various organic layers can be deposited sequentially,followed by a thin metal cathode. In zone 5, a thin film is deposited toencapsulate the OLED devices (via a thin film deposition technique as,for example, described in U.S. Pat. No. 7,968,146). Before substrate 310with encapsulated device (on device side 320) is wound upon retrievalroller 322, a film 340 may be laminated over device side 320 to furtherprotect the OLED devices and provide protection from mechanical damageincurred during the winding process. Lamination film 340 may have otherfunctionality including, for example, polarizers, AR films, lightextraction films such as diffusor or micro-lens array films, barriercoated films, and so on. In the illustrated embodiment, all depositionzones 3, 4 and 5 are under vacuum while other zones may optionally, andeven desirably, be under vacuum.

FIG. 7 illustrates another configuration of a system 300 c including thecomponents of system 300 and additional functionality. In that regard,system 300 c includes an inspection station or system and a treatmentstation or system in zone 6 thereof. One or more inspection stationsmay, for example, be added to different steps or processes in the OLEDprocess. In this example, an inspection station is added after thin filmencapsulation and before winding on retrieval roller 322. In addition, atreatment step may be incorporated after the inspection. For example,once a defect such as a particle is detected, certain treatments may beapplied to treat the defect. Such treatments include, for example, 1)marking the defect; 2) removing the defect (e.g., by laser); 3) removingthe area (cut a hole); and/or other methods. In a number of embodiments,all the deposition zones (3, 4, 5) are under vacuum, while other zonesmay also desirably be under vacuum.

FIGS. 4 through 7 illustrate processes and systems wherein substrate 310is moved generally horizontally and generally linearly. However,substrate 310 may be moved and supported in an arced or circular fashionas illustrated in FIGS. 8 and 9. FIG. 8 illustrates the process of FIG.5, performed around a generally circular roll coating roller 342. FIG. 9illustrates the process of FIG. 7, performed around a generally circularroll coating roller 342.

The systems hereof provide generally pristine interfaces for all thelayers of the OLED or other organic electronic devices. In embodimentswherein, for example, OLED deposition and encapsulation (and/or otherdepositions) occur without breaking vacuum, there is minimumcontamination at the interfaces, which provides for best possible deviceperformance in terms of device efficiency and lifetime. Because the thinfilm encapsulation directly encloses the OLEDs, both the top surface andthe edge of the devices are protected. Because all processes may beperformed continuously and without breaking vacuum, the handling ofsubstrate/device is minimized. The entire/completed device is rolled orwound only after encapsulation process, increasing the safety inhandling. In comparison, the method illustrated in FIG. 1 requiresrolling the device before moving to encapsulation process which cancause damage (including, for example, scratches and protrusions inmultiple layers due to particles).

Tension on the substrate in a roll-to-roll process provides excellentthermal contact between the substrate and a supporting fixture orfixtures, including electrodes and holders. This improvement in thermalcontact is independent of the deposition direction (for example, up ordown). In a number of embodiments, sufficient tension in the flexiblesubstrate is maintained to maintain direct contact between the flexiblesubstrate and a support therefor to facilitate thermal transfer (forexample, cooling) via thermal conduction between the support and thesubstrate in at least one of the plurality of zones. No mechanicalactuation is required with a continuous roll-to-roll process, and theregistration and alignment can be significantly simplified. Moreover, nolithography is required, significantly reducing the process time(including baking) and improve device performance (for example, byeliminating wet solution/water residue). As described above, highthroughput, which is controlled by web moving speed, is readily providedin a roll-to-roll process.

In a number of embodiments hereof, a vertical projection (in thedirection of gravity) of a perimeter of each one of the plurality ofdeposition sources used in forming organic electronic devices does notintersect the flexible substrate (wherein the flexible substrate is inmotion during the depositing the plurality of layers via a roll-to-rollfeed and retrieval system as described above). As used herein, the term“vertical” is defined as the direction aligned with the direction of theforce of gravity (for example, as evidenced by a plumb line). A plane is“horizontal” at a given point if it is perpendicular to the gradient ofthe gravity field at that point. In other words, if gravity makes aplumb bob hang perpendicular to the plane at that point, the plane ishorizontal. FIG. 10 illustrates a representative embodiment of novelprocess/system which reduces or minimizes particle contamination forproducing OLEDs using a roll-to-roll process. The position of thedeposition sources relative to the substrate set forth above greatlyreduces the likelihood of particles being transported from thedeposition sources to the substrate or any layer deposited or otherwiseformed thereon.

FIG. 10 illustrates a very simple system in which all deposition sourcesare placed below device surface 320 of substrate 310. In the illustratedsystem, deposition is performed under a vacuum condition in zone 2. Asdescribed above, zone 1 should be at least under controlled environmentto prevent the device to be contaminated by moisture and oxygen. Onceagain, it is desirable if zone 1 is also under vacuum. In the case of agenerally linear orientation of the substrate in a roll-to-roll process,deposition or device side 320 of substrate 310 may face down (in, forexample, a generally horizontal orientation of substrate 310) tominimize particle contamination (for example, as a result of gravity).The system of each of FIGS. 4 through 7 are also examples of such anorientation.

FIG. 11 illustrates a system including the components of the system ofFIG. 10 wherein the depositions are performed around generally circularroll coating roller 342. As described above, the vertical projection ofthe perimeter of each the plurality of deposition sources in FIG. 11does not intersect flexible substrate 310. This condition is notsatisfied in the systems of FIGS. 1, 8 and 9, for example. FIG. 12provides a schematic illustration of deposition sources 350 a through350 h positioned around generally circular roll coating roller 342. Thevertical projections of the perimeter of deposition source 350 a anddeposition source 350 b are illustrated by dashed arrows. In FIG. 12,the vertical projection of the perimeter of deposition source 350 aintersects flexible substrate 310, while the vertical projection of theperimeter of each of depositions sources 350 b through 350 h do notintersect flexible substrate 310. FIG. 13 illustrates an arrangement ofa system similar to that shown in FIG. 8 wherein the deposition sourcesare arranged such that the vertical projection of the perimeter of eachthe deposition sources does not intersect flexible substrate 310. FIG.14A illustrates an arrangement of a system similar to that shown in FIG.9 wherein the deposition sources are arranged such that the verticalprojection of the perimeter of each the deposition sources does notintersect flexible substrate 310. As illustrated in FIG. 14B, in anumber of embodiments, other equipment and/or systems such aspre-treatment equipment or systems in zone 2 and inspection/treatmentequipment or systems in zone 6 may be positioned such that the verticalprojections of the perimeters thereof do not intersect flexiblesubstrate 310 (thereby reducing the likelihood of particles beingtransported therefrom to the substrate or any layer deposited orotherwise formed thereon). FIG. 15 illustrates a system configurationwith two main rotation cylinders 342 a and 342 b wherein the depositionsources are arranged such that the vertical projection of the perimeterof each the deposition sources does not intersect flexible substrate310.

In a number of embodiments of devices, systems and methods hereof amaterial is deposited at less than atmospheric pressure onto a movingweb or substrate (in for example, a roll-to-roll process as describedabove) by delivering the material into an interior of at least onecylinder. The cylinder includes at least one opening therein throughwhich the material may pass to exit the interior of the cylinder. Thecylinder is rotated so that the material passes through the opening tobe deposited upon the moving web in a determined pattern. The materialmay, for example, be deposited at a pressure between approximately 10 to10⁻⁸ torr. In a number of embodiments, the material is deposited at apressure between approximately between 10⁻⁴ to 10⁻⁷ torr.

There are a number of advantages to using such a cylindrical mask fordepositing and patterning on a moving substrate. For example, acylindrical mask provides a method for depositing lines of materialperpendicular to the direction of the substrate web. The width of thelines may, for example, be controlled by a combination of the width ofthe opening or slit in the cylinder, the speed of the cylinder rotation,the direction of the cylinder rotation and the speed of the substrateweb. The spacing between the lines may, for example, be controlled bythe number/spacing of openings in the cylinder and the rotational speed.Lines and/or patterns that are not perpendicular to direction of the webmay also be deposited. By, for example, using more than one concentriccylinders and controlling their speed and other parameters, one maydeposit not only straight lines but a design-like pattern on asubstrate. Use of a cylindrical mask provides a non-contact method fordepositing lines (for example, buss lines), thereby reducing particulatecontamination as compared to contact methods. All material beingdeposited may be contained within the cylinder, thereby reducing oreliminating shielding. Moreover, the patterning features/characteristicsare readily programmable.

As described above, OLED and other organic electronic devices includeseveral layers of materials. These layers may include a bottom electrode(anode), an organic stack, and a top electrode (cathode). Typically,multiple OLED devices are formed on the substrate, which may be arrangedin directions both parallel and perpendicular to the direction of motionof the substrate. This manufacturing process requires the patterning ofOLEDs including electrodes and organic layers. Another feature in OLEDsis a metal bus line. For bottom emission OLED lighting panels, the anodemay, for example, be made using a transparent conductor such as ITO.When the transparent conductor is used for a large area lighting panel,however, the panel often looks non-uniform. This effect is a result ofthe sheet resistance of the transparent conductor being significantlyhigher than a metal conductor. To reduce the non-uniformity, conductivebuss lines (typically metal) are used over the transparent conductor toimprove the conductivity of the bottom electrode.

Depositing metal buss lines 350 (see FIG. 16) in the direction of themoving substrate 310 may be done using several different methods. Onemethod is to flash evaporate the metal material 400 under a slit or hole420 at programed times to produce a uniform line in the direction of themoving substrate as illustrated in FIG. 16. Another method would be tohave continuous evaporation through a hole or slit to create acontinuous metal line on the substrate. Multiple holes or slits may beused to create an array of buss lines on the substrate. Breaks in theline may be achieved by using a removable material attached to thesubstrate to mask the metal from being deposited where it is notdesired.

Depositing buss lines perpendicular to a moving substrate web may, forexample, be made by either flash evaporating or continuous evaporating aconductive material (metal) through a cylindrical mask onto thesubstrate as discussed above. As, for example, illustrated in FIG. 17A,the cylindrical mask may, for example, include a cylinder 500 which hasone or more narrow slit(s) 510 therein and has, for example, anevaporative source 400 within the interior of cylinder 500. Cylinder 500rotates around evaporative source 400. The material passes through slit510 onto the substrate web 310 (see FIG. 17B) when slit 510 reaches aspecific location during the rotation of cylinder 500. The slit locationfor deposition may, for example, be directly above source 400, but otherlocations may be used. A shield may be used to confine the evaporatedsource material so that it can only go certain direction e.g. upward. Asdescribed above, a combination of the width of slit 510, the speed ofthe cylinder rotation, the direction of the cylinder rotation and thespeed of the substrate web may be used to determine the width of, forexample, a buss line. The length of slit or opening 510 may, forexample, go from one edge of the substrate to the other or there may beseveral breaks in the slit if shorter buss (or other) lines are desired.There may be multiple slits 510 a (see FIG. 17B) around thecircumference of a cylinder 500 a to reduce the rotation speed ofcylinder 500 a as shown in FIG. 17B. The cylinder rotation speed may bereadily programmable to provide a required distance between, forexample, buss lines.

Additionally, slits in a cylindrical mask may be made that are parallelto the direction of the moving substrate to provide patterned lines inthe direction of the web. Slits parallel to the moving substrate may,for example, provide a method for blocking the deposition in undesirableareas (for example, in between lighting panels). When using both thepatterning method for the parallel and perpendicular buss lines, arepeatable grid pattern of buss lines may be deposited for each lightingpanel as, for example, illustrated in FIG. 18.

Another option is to have a pattern of slits or holes in the cylinder.The pattern on the substrate may, for example, have a dual function. Forexample, a first function may be a buss line to improve uniformity ofthe lighting panel. A second function may be a decorative feature(pattern) to the lighting panel. The methods described above may be alsoused for organic deposition, as shown, for example, in FIG. 19. In suchan application, cylinder 600 may, for example, include large open areas610 for the organic material within cylinder 600 to be deposited andsmaller blocked areas 620 to prevent the organic material from beingdeposited onto undesirable areas, such as the contacts or between eachlighting panel. This system and method reduce the requirement formasking to be applied directly to substrate 310 prior to the depositionprocess.

Providing a determined pattern including a two-dimensional matrix on asubstrate may, for example, be accomplished in different ways. In afirst method, the substrate may, for example, begin with a parallelpattern (a series of lines in the direction of the moving substrate).The parallel pattern may, for example, be deposited using a firstcylindrical mask. The substrates then may pass over a cylinder wherein aperpendicular pattern (for example, a line perpendicular to the movingsubstrate) are deposited creating a two-dimensional matrix asillustrated in FIG. 20. In another method, a two dimensional matrix isdeposited through a single cylinder at one time (that is, the pattern ofopenings in the cylinder forms a two-dimensional matrix). This isrelatively simple when there is only one vertical or only one horizontalopening in the cylinder as illustrated in FIG. 21. When more than onevertical line and more than one horizontal line are desired, the areabetween the vertical and horizontal openings in the cylinder will needto be supported from inside the cylinder. The cylinder wall alone cannotsupport such area because the opening in the cylinder completelysurrounds that area (see FIG. 22).

This disclosure has been presented for purposes of illustration anddescription but is not intended to be exhaustive or limiting. Manymodifications and variations will be apparent to those of ordinary skillin the art. The example embodiments were chosen and described in orderto explain principles and practical application, and to enable others ofordinary skill in the art to understand the disclosure for variousembodiments with various modifications as are suited to the particularuse contemplated.

Thus, although illustrative example embodiments have been describedherein with reference to the accompanying figures, it is to beunderstood that this description is not limiting and that various otherchanges and modifications may be affected therein by one skilled in theart without departing from the scope or spirit of the disclosure.

1-44. (canceled)
 45. A system for depositing a material onto a movingsubstrate web, comprising: a system for moving the web; a cylindercomprising at least one opening therein through which the materialwithin an interior of the cylinder may pass to exit the interior of thecylinder at less than atmospheric pressure; and a control system torotate the cylinder in a controlled manner so that the material passesthrough the at least one opening to be deposited upon the moving web ina determined pattern.
 46. The method of claim 45, wherein the materialis deposited at a pressure between 10 to 10⁻⁸ torr.
 47. The method ofclaim 45, wherein the material is deposited at a pressure between 10⁻⁴to 10⁻⁷ torr.
 48. The method of claim 45, wherein a source of thematerial is positioned within the cylinder.
 49. The method of claim 45,wherein an axis of the cylinder is generally perpendicular to adirection of motion of the web.
 50. The method of claim 45, whereinmicroelectronic systems are formed on the web.
 51. The method of claim50, wherein the material is an organic material.
 52. The method of claim50, wherein the material is a conductive material.
 53. The method ofclaim 52, wherein the determined pattern comprises bus lines over atransparent conductor on the web.
 54. A substrate web having adetermined pattern formed by the process of: delivering the materialinto an interior of at least one cylinder, the cylinder comprising atleast one opening therein through which the material may pass to exitthe interior of the cylinder; and rotating the cylinder so that thematerial passes through the at least one opening to be deposited uponthe web in the determined pattern as the web is moving, wherein thematerial is deposited upon the web at a pressure less than atmosphericpressure.
 55. The method of claim 54, wherein the pressure is between 10to 10⁻⁸ torr.
 56. The method of claim 54, wherein the pressure isbetween 10⁻⁴ to 10⁻⁷ torr.
 57. The method of claim 54, wherein a sourceof the material is positioned within the cylinder.
 58. The method ofclaim 54, wherein an axis of the cylinder is generally perpendicular toa direction of motion of the web.
 59. The method of claim 54, whereinmicroelectronic systems are formed on the web.
 60. The method of claim59, wherein the material is an organic material.
 61. The method of claim59, wherein the material is a conductive material.
 62. The method ofclaim 61, wherein the determined pattern comprises bus lines over atransparent conductor on the web.